1-vinyltriazole compounds and plant growth and fungicidal compositions

ABSTRACT

1-Vinyltriazole compounds of the formula ##STR1## wherein R 1  is alkyl, substituted alkyl, cycloalkyl, aryl or substituted aryl; 
     R 2  is alkyl; 
     R 3  is alkyl, cycloalkyl, cycloalkenyl, substituted cycloalkenyl, alkenyl, aryl or substituted aryl; or 
     R 2  and R 3 , together with the carbon to which they are bonded, represent cycloalkenyl, substituted cycloalkenyl, cycloalkyl or substituted cycloalkyl; 
     is the group ##STR2##  or, alternatively, X may represent a keto group provided that when X is a keto group, R 1  is alkyl, substituted alkyl, cycloalkyl, or substituted cycloalkyl; 
     R 4  is hydrogen, alkyl, aralkyl, substituted aralkyl, acyl, carbamoyl or substituted carbamoyl; 
     R 5  is hydrogen, alkyl, aralkyl or substituted aralkyl; 
     and acid addition salts and metal salt complexes thereof; are outstandingly effective plant growth regulants and as fungicides.

This application is a continuation of application Ser. No. 587,036,filed Mar. 7, 1984, now abandoned, which is a division of Ser. No.294,603, filed Aug. 20, 1981, now U.S. Pat. No. 4,486,218, which is acontinuation in part of Ser. No. 112,891, filed Jan. 17, 1980, nowabandoned.

This invention relates to certain 1-vinyltriazole compounds, to plantgrowth regulant compositions and fungicidal compositions containingthem, and to methods for regulating plant growth and for combatingfungi.

It is known that certain 2-haloethyl-trialkyl-ammonium halides haveplant growth regulating properties (see U.S. Pat. No. 3,156,554). Thus,for example, an influencing of plant growth, in particular an inhibitionof vegetative plant growth, can be achieved in important crop plantswith the aid of 2-chloroethyl-trimethylammonium chloride. However, theactivity of this substance is not always adequate, especially when smallamounts are used.

It is also known that 2-chloroethylphosphonic acid has a plant growthregulating action (see DE-OS (German Published Specification) No.1,667,968). However, the results achieved with this substance arelikewise not always satisfactory.

Furthermore, it is known that acylated and carbamoylated derivatives of3,3-dimethyl-1-phenoxy-1-triazolyl-butan-2-ols, which are substituted inthe phenyl part, have a good fungicidal activity (see DE-OS (GermanPublished Specification) No. 2,600,799). Certain4,4-dimethyl-1-phenyl-2-triazolyl-pentan-3-ones, which are substitutedin the phenyl part, for example,1-(4-chlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-pentan-3-one, arelikewise suitable for combating fungi (see DE-OS (German PublishedSpecification) No. 2,734,426). However, the action of these azolederivatives is not always completely satisfactory, especially when smallamounts and low concentrations are used.

The present invention now provides, as new compounds, the1-vinyl-triazole derivatives of the formula ##STR3## in which R¹represents optionally substituted alkyl, cycloalkyl or optionallysubstituted aryl,

R² represents alkyl and

R³ represents alkyl, cycloalkyl, optionally substituted cycloalkenyl,alkenyl or optionally substituted aryl, or

R² and R³, together with the carbon atom to which they are bonded,represent optionally substituted cycloalkenyl or cycloalkyl,

X represents the group ##STR4## or alternatively may represent the ketogroup provided that R¹ represents optionally substituted alkyl orcycloalkyl,

R⁴ represents hydrogen, alkyl, optionally substituted aralkyl, acyl oroptionally substituted carbamoyl, and

R⁵ represents hydrogen, alkyl or optionally substituted aralkyl,

and acid addition salts and metal salt complexes thereof.

It has been found that the 1-vinyltriazole derivatives of the formula(I) and acid addition salts and metal salt complexes thereof havepowerful plant growth regulating properties and powerful fungicidalproperties.

Preferably, in formula (I), R¹ represents straight-chain or branchedalkyl with 1 to 4 carbon atoms [which optionally carries one or twosubstituents selected independently from, preferably, halogen,alkylcarbonyloxy with 1 to 4 carbon atoms in the alkyl part,alkylsulphonyloxy with 1 to 4 carbon atoms and phenylsulphonyloxy whichis itself optionally substituted by halogen or by alkyl with 1 to 4carbon atoms], cycloalkyl with 5 to 7 carbon atoms or aryl with 6 to 10carbon atoms (such as phenyl or naphthyl) [which aryl optionally carriesone or more substituents selected independently from, preferably,halogen, alkyl with 1 to 4 carbon atoms, phenyl, phenoxy, halophenyl andhalophenoxy],

R² represents straight-chain or branched alkyl with 1 to 4 carbon atoms,and

R³ represents straight-chain or branched alkyl with 1 to 4 carbon atoms,cycloalkyl with 5 to 7 carbon atoms, cycloalkenyl with 5 to 7 carbonatoms [which is optionally substituted by alkyl with 1 to 4 carbonatoms], alkenyl with 2 to 4 carbon atoms or aryl with 6 to 10 carbonatoms (such as phenyl or naphthyl) [which is optionally substituted by,preferably, halogen or alkyl with 1 to 4 carbon atoms], or

R² and R³, together with the carbon atom to which they are bonded,represent cycloalkenyl with 5 to 7 carbon atoms [which is optionallysubstituted by alkyl with 1 to 4 carbon atoms] or cycloalkyl with 3 to 7carbon atoms,

X represents the group --C(OR⁴)R⁵ --, or may represent the keto groupprovided R¹ represents optionally substituted alkyl or cycloalkyl,

R⁴ represents hydrogen, straight-chain or branched alkyl with 1 to 4carbon atoms, aralkyl with 1 to 2 carbon atoms in the alkyl part and 6to 10 carbon atoms in the aryl part (such as benzyl or naphthylmethyl)[which optionally carries one or more substituents selectedindependently from, preferably, halogen, alkyl with 1 to 4 carbon atoms,haloalkyl with up to 2 carbon atoms and up to 3 identical or differenthalogen atoms (preferred halogen atoms being fluorine and chlorine) andphenyl and phenoxy, the last two being themselves optionally substitutedby halogen], the acyl radical --CO--R¹⁰ or the carbamoyl radical--CO--NR¹¹ R¹²,

R⁵ represents hydrogen, alkyl with 1 to 4 carbon atoms or aralkyl with 1to 2 carbon atoms in the alkyl part and 6 to 10 carbon atoms in the arylpart (such as benzyl) [which is optionally substituted by halogen oralkyl with 1 to 4 carbon atoms],

R¹⁰ represents straight-chain or branched alkyl with 1 to 4 carbonatoms, haloalkyl with 1 to 2 carbon atoms and 1 to 5 identical ordifferent halogen atoms (preferably fluorine and chlorine atoms) orphenyl or benzyl [either of which is optionally substituted by,preferably, halogen or alkyl with 1 to 4 carbon atoms],

R¹¹ represents hydrogen or alkyl with 1 to 4 carbon atoms, and

R¹² represents alkyl with 1 to 8 carbon atoms, haloalkyl with up to 4carbon atoms and up to 5 identical or different halogen atoms(especially fluorine or chlorine atoms), aryl with 6 to 10 carbon atoms(such as phenyl or naphthyl) [which optionally carries one or moresubstituents selected independently from, preferably, halogen, alkylwith 1 to 4 carbon atoms and haloalkyl with up to 2 carbon atoms and upto 5 identical or different halogen atoms (especially fluorine andchlorine atoms)] or haloalkylmercapto with 1 to 2 carbon atoms and up to5 halogen atoms (especially fluorine and chlorine atoms).

The compounds of the formula (I) can exist in two geometric isomerforms, depending on the arrangement of the groups which are bonded tothe double bond. If X represents the group --C(OR⁴)R⁵ --, an asymmetriccarbon atom is present, so that in this case the compounds of theformula (I) are also obtained in two optical isomer forms. The formula(I) therefore embraces both the individual isomers and the isomermixtures.

The invention also provides a process for the preparation of a1-vinyltriazole derivative of the formula (I), or an acid addition saltor metal salt complex thereof, in which

(a) a triazole-ketone of the general formula ##STR5## in which R¹ hasthe meaning indicated above,

is reacted with an aldehyde of the general formula ##STR6## in which R²and R³ have the meanings indicated above, in the presence of a solventand in the presence of a catalyst, and from the isomers which form, as aresult of splitting off of water, the desired isomeric product of thegeneral formula ##STR7## in which R¹, R² and R³ have the meaningsindicated above,

is isolated by customary methods, or

(b) a compound, obtainable by process variant (a), of the generalformula ##STR8## in which R¹, R² and R³ have the meanings indicatedabove is either

(α) reduced with a complex hydride in the presence of a solvent, or

(β) reduced with a Grignard compound of the general formula

    R.sup.6 --Mg--Hal                                          (IV),

in which

R⁶ represents alkyl or optionally substituted aralkyl and

Hal represents halogen,

in the presence of a solvent, or

(c) a compound, obtainable by process variant (b)(α) or (b)(β), of thegeneral formula ##STR9## in which R¹, R², R³ and R⁵ have the meaningsindicated above, is reacted with a halide of the general formula

    R.sup.7 --Hal'                                             (V),

in which

R⁷ represents alkyl, optionally substituted aralkyl, acyl or optionallysubstituted carbamoyl and

Hal' represents halogen,

in the presence of a solvent, and if appropriate in the presence of astrong base or if appropriate in the presence of an acid-binding agent,or

(d) a compound, obtainable by process variant (b)(α) or (b)(β), of thegeneral formula ##STR10## in which R¹, R², R³ and R⁵ have the meaningsindicated above, is reacted with an acid anhydride of the generalformula

    R.sup.8 --O--R.sup.8                                       (VI),

in which

R⁸ represents acyl,

in the presence of a solvent and if appropriate in the presence of acatalyst, or

(e) a compound obtainable by process variant (b)(α) or (b)(β), of thegeneral formula ##STR11## is reacted with an isocyanate of the generalformula

    O═C═N--R.sup.9                                     (VII),

in which

R⁹ represents alkyl, haloalkyl or optionally substituted aryl,

in the presence of a solvent and if appropriate in the presence of acatalyst,

and, if required, an acid or a metal salt is then added onto thecompound obtained by any of process variants (a) to (e).

Surprisingly, the 1-vinyltriazoles according to the invention and acidaddition salts and metal salt complexes thereof exhibit a better plantgrowth regulating action than the known 2-chloroethyl-trimethylammoniumchloride and 2-chloroethylphosphonic acid, which is likewise known,which are recognized as substances of the same type of action which havea good activity. Surprisingly, the compounds according to the inventionalso have a better fungicidal action than the acylated and carbamoylatedderivatives of 3,3-dimethyl-1-phenoxy-1-triazolyl-butan-2-olssubstituted in the phenyl part, which are known from the state of theart, and than1-(4-chlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-pentan-3-one,which is likewise known, which are closely related compounds chemicallyand from the point of view of their action. The active compoundsaccording to the invention thus represent an enrichment of the art.

Those compounds of the formula (I) are especially preferred in which R¹represents tert.-butyl, isopropyl, chloro-tert.-butyl,bromo-tert.-butyl, fluoro-tert.-butyl, acetoxy-tert.-butyl,methylsulphonyloxy-tert.-butyl, p-toluenesulphonyloxy-tert.-butyl,1,3-dichloro-2-methyl-prop-2-yl, 1,3-dibromo-2-methyl-prop-2-yl,1,3-difluoro-2-methyl-prop-2-yl, 1-chloro-3-bromo-2-methyl-prop-2-yl,1,3-diacetoxy-2-methyl-prop-2-yl, cyclohexyl, phenyl, chlorophenyl,bromphenyl, dichlorophenyl, fluorophenyl, methylphenyl, dimethylphenyl,chloro-methylphenyl, biphenylyl, phenoxyphenyl, chlorophenylphenyl orchlorophenoxyphenyl; R² represents methyl, ethyl, propyl or butyl and R³represents methyl, ethyl, isopropyl, cyclohexyl, cyclohexenyl,methylcyclohexenyl, allyl, methacryl, phenyl, chlorophenyl,dichlorophenyl or methylphenyl; or R² and R³, together with the carbonatom to which they are bonded, represent cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cyclohexenyl or methylcyclohexenyl; Xrepresents the group --C(OR⁴)R⁵, or alternatively the keto group,provided R¹ has the optionally substituted alkyl or cycloalkyl meaningsindicated, R⁴ represents hydrogen, methyl, ethyl, n-propyl, isopropyl,isobutyl, naphthyl which is optionally substituted by chlorine, benzylwhich is optionally monosubstituted or polysubstituted by identical ordifferent substituents from the group consisting of chlorine, fluorine,methyl, phenyl, chlorophenyl, phenoxy and chlorophenoxy, the acylradical --CO--R¹⁰ or the carbamoyl radical --CO--NR¹¹ R¹² ; R⁵represents hydrogen, methyl, ethyl, isopropyl, benzyl, chlorobenzyl ordichlorobenzyl; R¹⁰ represents methyl, ethyl, isopropyl, isobutyl,chloromethyl, dichloromethyl or phenyl or benzyl, either of which isoptionally monosubstituted or polysubstituted, the substituents beingchlorine, bromine or methyl; R¹¹ represents hydrogen, methyl or ethyl;and R¹² represents methyl, ethyl, chloroethyl, phenyl, chlorophenyl,trifluoromethyl, chlorodifluoro-methyl, dichloro-fluoromethyl ortrichloromethyl-mercapto.

The following compounds of the general formula (I) may be mentionedspecifically, in addition to the compounds mentioned later in thepreparative examples:

    ______________________________________                                         ##STR12##                    (Ia)                                            R.sup.1                R.sup.2 R.sup.3                                        ______________________________________                                        C(CH.sub.3).sub.3      C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                C(CH.sub.3).sub.3      C.sub.2 H.sub.5                                                                       CH.sub.3                                       C(CH.sub.3).sub.3      CH.sub.3                                                                              CH.sub.3                                       C(CH.sub.3).sub.3      CH.sub.3                                                                               ##STR13##                                     C(CH.sub.3).sub.3      CH.sub.3                                                                               ##STR14##                                     C(CH.sub.3).sub.3      Cyclopropyl                                            C(CH.sub.3).sub.3      Cyclobutyl                                             C(CH.sub.3).sub.3      Cyclopentyl                                            C(CH.sub.3).sub.3      Cycloheptyl                                            C(CH.sub.3).sub.3      Norbon-3-en-2-yl                                        ##STR15##             Cyclohexane                                             ##STR16##             Cyclohexene                                             ##STR17##             Methylcyclohexene                                       ##STR18##             CH.sub.3                                                                              CH.sub.3                                        ##STR19##             Cyclohexane                                             ##STR20##             Cyclohexene                                             ##STR21##             Methylcyclohexene                                       ##STR22##             Methylcyclohexene                                       ##STR23##             CH.sub.3                                                                              CH.sub.3                                        ##STR24##             Cyclohexane                                             ##STR25##             Cyclohexene                                             ##STR26##             Methylcyclohexene                                       ##STR27##             CH.sub.3                                                                              CH.sub.3                                        ##STR28##             Cyclohexane                                             ##STR29##             Cyclohexene                                             ##STR30##             Methylcyclohexene                                       ##STR31##             CH.sub.3                                                                              CH.sub.3                                        ##STR32##             Cyclohexane                                             ##STR33##             Cyclohexene                                             ##STR34##             Methylcyclohexene                                       ##STR35##             CH.sub.3                                                                              CH.sub.3                                        ##STR36##             Cyclohexane                                             ##STR37##             Cyclohexene                                             ##STR38##             Methylcyclohexene                                       ##STR39##             CH.sub.3                                                                              CH.sub.3                                        ##STR40##             Cyclohexane                                             ##STR41##             Cyclohexene                                             ##STR42##             Methylcyclohexene                                       ##STR43##             CH.sub.3                                                                              CH.sub.3                                        ##STR44##             Cyclohexane                                             ##STR45##             Cyclohexene                                             ##STR46##             Methylcyclohexene                                       ##STR47##             CH.sub.3                                                                              CH.sub.3                                        ##STR48##             Cyclohexane                                             ##STR49##             Cyclohexene                                             ##STR50##             Methylcyclohexene                                       ##STR51##             CH.sub.3                                                                              CH.sub.3                                       ______________________________________                                    

    __________________________________________________________________________     ##STR52##                           (Ib)                                     R.sup.1             R.sup.2                                                                           R.sup.3                                                                             R.sup.5                                         __________________________________________________________________________    C(CH.sub.3).sub.3   C.sub.2 H.sub.5                                                                   CH.sub.3                                                                            H                                               C(CH.sub.3).sub.3   CH.sub.3                                                                          CH.sub.3                                                                            H                                               C(CH.sub.3).sub.3   CH.sub.3                                                                           ##STR53##                                                                          H                                               C(CH.sub.3).sub.3   CH.sub.3                                                                           ##STR54##                                                                          H                                               C(CH.sub.3).sub.3   Cyclopropyl                                                                             H                                               C(CH.sub.3).sub.3   Cyclobutyl                                                                              H                                               C(CH.sub.3).sub.3   Cyclopentyl                                                                             H                                               C(CH.sub.3).sub.3   Cycloheptyl                                                                             H                                               C(CH.sub.3).sub.3   CH.sub.3                                                                          CH.sub.3                                                                            CH.sub.3                                        C(CH.sub.3).sub.3   Cyclohexane                                                                             CH.sub.3                                        C(CH.sub.3).sub.3   Cyclohexene                                                                             CH.sub.3                                        C(CH.sub.3).sub.3   Methylcyclohexene                                                                       CH.sub.3                                        C(CH.sub.3).sub.3   CH.sub.3                                                                          CH.sub.3                                                                             ##STR55##                                      C(CH.sub.3).sub.3   Cyclohexane                                                                              ##STR56##                                      C(CH.sub.3).sub.3   Cyclohexene                                                                              ##STR57##                                      C(CH.sub.3).sub.3   Methylcyclohexene                                                                        ##STR58##                                       ##STR59##          CH.sub.3                                                                          CH.sub.3                                                                            H                                                ##STR60##          Cyclohexane                                                                             H                                                ##STR61##          Cyclohexene                                                                             H                                                ##STR62##          Methylcyclohexene                                                                       H                                                ##STR63##          CH.sub.3                                                                          CH.sub.3                                                                            H                                                ##STR64##          Cyclohexane                                                                             H                                                ##STR65##          Cyclohexene                                                                             H                                                ##STR66##          Methylcyclohexene                                                                       H                                                ##STR67##          CH.sub.3                                                                          CH.sub.3                                                                            H                                                ##STR68##          Cyclohexane                                                                             H                                                ##STR69##          Cyclohexene                                                                             H                                                ##STR70##          Methylcyclohexene                                                                       H                                                ##STR71##          CH.sub.3                                                                          CH.sub.3                                                                            H                                                ##STR72##          Cyclohexane                                                                             H                                                ##STR73##          Cyclohexene                                                                             H                                                ##STR74##          Methylcyclohexene                                                                       H                                                ##STR75##          CH.sub.3                                                                          CH.sub.3                                                                            H                                                ##STR76##          Cyclohexane                                                                             H                                                ##STR77##          Cyclohexene                                                                             H                                                ##STR78##          Methylcyclohexene                                                                       H                                                ##STR79##          CH.sub.3                                                                          CH.sub.3                                                                            H                                                ##STR80##          Cyclohexane                                                                             H                                                ##STR81##          Cyclohexene                                                                             H                                                ##STR82##          Methylcyclohexene                                                                       H                                                ##STR83##          CH.sub.3                                                                          CH.sub.3                                                                            H                                                ##STR84##          Cyclohexane                                                                             H                                                ##STR85##          Cyclohexene                                                                             H                                                ##STR86##          Methylcyclohexene                                                                       H                                                ##STR87##          CH.sub.3                                                                          CH.sub.3                                                                            H                                                ##STR88##          Cyclohexane                                                                             H                                                ##STR89##          Cyclohexene                                                                             H                                                ##STR90##          Methylcyclohexene                                                                       H                                                ##STR91##          CH.sub.3                                                                          CH.sub.3                                                                            H                                                ##STR92##          Cyclohexane                                                                             H                                                ##STR93##          Cyclohexene                                                                             H                                                ##STR94##          Methylcyclohexene                                                                       H                                                ##STR95##          CH.sub.3                                                                          CH.sub.3                                                                            H                                                ##STR96##          Cyclohexane                                                                             H                                                ##STR97##          Cyclohexene                                                                             H                                                ##STR98##          Methylcyclohexene                                                                       H                                                ##STR99##          CH.sub.3                                                                          CH.sub.3                                                                            H                                                ##STR100##         Cyclohexane                                                                             H                                                ##STR101##         Cyclohexene                                                                             H                                                ##STR102##         Methylcyclohexene                                                                       H                                               __________________________________________________________________________

    ______________________________________                                         ##STR103##                   (Ic)                                            R.sup.1    R.sup.2 R.sup.3                                                                         R.sup.4          R.sup.5                                 ______________________________________                                        C(CH.sub.3).sub.3                                                                        CH.sub.3 CH.sub.3                                                                       C.sub.2 H.sub.5  H                                       C(CH.sub.3).sub.3                                                                        Cyclohex- C.sub.2 H.sub.5  H                                                  ane                                                                C(CH.sub.3).sub.3                                                                        Cyclohex- C.sub.2 H.sub.5  H                                                  ene                                                                C(CH.sub.3).sub.4                                                                        Methylcy- C.sub.2 H.sub.5  H                                                  clohexene                                                           ##STR104##                                                                              CH.sub.3 CH.sub.3                                                                       C.sub.2 H.sub.5  CH.sub.3                                 ##STR105##                                                                              Cyclohex- ane                                                                           C.sub.2 H.sub.5  CH.sub.3                                 ##STR106##                                                                              Cyclohex- ene                                                                           C.sub.2 H.sub.5  CH.sub.3                                 ##STR107##                                                                              Methylcy- clohexene                                                                     C.sub.2 H.sub.5  CH.sub.3                                 ##STR108##                                                                              CH.sub.3 CH.sub.3                                                                       C.sub.2 H.sub.5  H                                        ##STR109##                                                                              Cyclohex- ane                                                                           C.sub.2 H.sub.5  H                                        ##STR110##                                                                              Cyclohex- ene                                                                           C.sub.2 H.sub.5  H                                        ##STR111##                                                                              Methylcy- clohexene                                                                     C.sub.2 H.sub.5  H                                        ##STR112##                                                                              CH.sub.3 CH.sub.3                                                                       C.sub.2 H.sub.5  H                                        ##STR113##                                                                              Cyclohex- ane                                                                           C.sub.2 H.sub.5  H                                        ##STR114##                                                                              Cyclohex- ene                                                                           C.sub.2 H.sub.5  H                                        ##STR115##                                                                              Methylcy- clohexene                                                                     C.sub.2 H.sub.5  H                                       C(CH.sub.3).sub.3                                                                        CH.sub.3 CH.sub.3                                                                        ##STR116##      H                                       C(CH.sub.3).sub.3                                                                        Cyclohex- ane                                                                            ##STR117##      H                                       C(CH.sub.3).sub.3                                                                        Cyclohex- ene                                                                            ##STR118##      H                                       C(CH.sub.3).sub.3                                                                        Methylcy- clohexene                                                                      ##STR119##      H                                        ##STR120##                                                                              CH.sub.3 CH.sub.3                                                                        ##STR121##      H                                        ##STR122##                                                                              Cyclohex- ane                                                                            ##STR123##      H                                        ##STR124##                                                                              Cyclohex- ene                                                                            ##STR125##      H                                        ##STR126##                                                                              Methylcy- clohexene                                                                      ##STR127##      H                                        ##STR128##                                                                              CH.sub.3 CH.sub.3                                                                        ##STR129##      H                                        ##STR130##                                                                              Cyclohex- ane                                                                            ##STR131##      H                                        ##STR132##                                                                              Cyclohex- ene                                                                            ##STR133##      H                                        ##STR134##                                                                              Methylcy- clohexene                                                                      ##STR135##      H                                        ##STR136##                                                                              CH.sub.3 CH.sub. 3                                                                       ##STR137##      H                                        ##STR138##                                                                              Cyclohex- ane                                                                            ##STR139##      H                                        ##STR140##                                                                              Cyclohex- ene                                                                            ##STR141##      H                                        ##STR142##                                                                              Methylcy- clohexene                                                                      ##STR143##      H                                        ##STR144##                                                                              CH.sub.3 CH.sub.3                                                                       COCH.sub.3       H                                        ##STR145##                                                                              Cyclohex- ane                                                                           COCH.sub.3       H                                        ##STR146##                                                                              Cyclohex- ene                                                                           COCH.sub.3       H                                        ##STR147##                                                                              Methylcy- clohexene                                                                     COCH.sub.3       H                                        ##STR148##                                                                              CH.sub.3 CH.sub.3                                                                       COCH.sub.3       H                                        ##STR149##                                                                              Cyclohex- ane                                                                           COCH.sub.3       H                                        ##STR150##                                                                              Cyclohex- ene                                                                           COCH.sub.3       H                                        ##STR151##                                                                              Methylcy- clohexene                                                                     COCH.sub.3       H                                        ##STR152##                                                                              CH.sub.3 CH.sub.3                                                                       COCH.sub.3       H                                        ##STR153##                                                                              Cyclohex- ane                                                                           COCH.sub.3       H                                        ##STR154##                                                                              Cyclohex- ene                                                                           COCH.sub.3       H                                        ##STR155##                                                                              Methylcy- clohexene                                                                      COCH.sub.3      H                                        ##STR156##                                                                              CH.sub.3 CH.sub.3                                                                       CONHCH.sub.3     H                                        ##STR157##                                                                              Cyclohex- ane                                                                           CONHCH.sub.3     H                                        ##STR158##                                                                              Cyclohex- ene                                                                           CONHCH.sub.3     H                                        ##STR159##                                                                              Methylcy- clohexene                                                                     CONHCH.sub.3     H                                        ##STR160##                                                                              CH.sub.3 CH.sub.3                                                                       CONHCH.sub.3     H                                        ##STR161##                                                                              Cyclohex- ane                                                                           CONHCH.sub.3     H                                        ##STR162##                                                                              Cyclohex- ene                                                                           CONHCH.sub.3     H                                        ##STR163##                                                                              Methylcy- clohexene                                                                     CONHCH.sub.3     H                                        ##STR164##                                                                              CH.sub.3 CH.sub.3                                                                       CONHCH.sub.3     H                                        ##STR165##                                                                              Cyclohex- ane                                                                           CONHCH.sub.3     H                                        ##STR166##                                                                              Cyclohex- ene                                                                           CONHCH.sub.3     H                                        ##STR167##                                                                              Methylcy- clohexene                                                                     CONHCH.sub.3     H                                        ##STR168##                                                                              CH.sub.3 CH.sub.3                                                                        ##STR169##      H                                        ##STR170##                                                                              Cyclohex- ane                                                                            ##STR171##      H                                        ##STR172##                                                                              Cyclohex- ene                                                                            ##STR173##      H                                        ##STR174##                                                                              Methylcy- clohexene                                                                      ##STR175##      H                                        ##STR176##                                                                              CH.sub.3 CH.sub.3                                                                        ##STR177##      H                                        ##STR178##                                                                              Cyclohex- ane                                                                            ##STR179##      H                                        ##STR180##                                                                              Cyclohex- ene                                                                            ##STR181##      H                                        ##STR182##                                                                              Methylcy- clohexene                                                                      ##STR183##      H                                        ##STR184##                                                                              CH.sub.3 CH.sub.3                                                                        ##STR185##      H                                        ##STR186##                                                                              Cyclohex- ane                                                                            ##STR187##      H                                        ##STR188##                                                                              Cyclohex- ene                                                                            ##STR189##      H                                        ##STR190##                                                                              Methylcy- clohexene                                                                      ##STR191##      H                                        ##STR192##                                                                              CH.sub.3 CH.sub.3                                                                        ##STR193##      H                                        ##STR194##                                                                              Cyclohex- ane                                                                            ##STR195##      H                                        ##STR196##                                                                              Cyclohex- ene                                                                            ##STR197##      H                                        ##STR198##                                                                              Methylcy- clohexene                                                                      ##STR199##      H                                        ##STR200##                                                                              CH.sub.3 CH.sub.3                                                                        ##STR201##      H                                        ##STR202##                                                                              Cyclohex- ane                                                                            ##STR203##      H                                        ##STR204##                                                                              Cyclohex- ene                                                                            ##STR205##      H                                        ##STR206##                                                                              Methylcy- clohexene                                                                      ##STR207##      H                                        ##STR208##                                                                              CH.sub.3 CH.sub.3                                                                        ##STR209##      H                                        ##STR210##                                                                              Cyclohex- ane                                                                            ##STR211##      H                                        ##STR212##                                                                              Cyclohex- ene                                                                            ##STR213##      H                                        ##STR214##                                                                              Methylcy- clohexene                                                                      ##STR215##      H                                        ##STR216##                                                                              CH.sub.3 CH.sub.3                                                                       COCHCl.sub.2     H                                        ##STR217##                                                                              Cyclohex- ane                                                                           COCHCl.sub.2     H                                        ##STR218##                                                                              Cyclohex- ene                                                                           COCHCl.sub.2     H                                        ##STR219##                                                                              Methylcy- clohexene                                                                     COCHCl.sub.2     H                                        ##STR220##                                                                              CH.sub.3 CH.sub.3                                                                       COCHCl.sub.2     H                                        ##STR221##                                                                              Cyclohex- ane                                                                           COCHCl.sub.2     H                                        ##STR222##                                                                              Cyclohex- ene                                                                           COCHCl.sub.2     H                                        ##STR223##                                                                              Methylcy- clohexene                                                                     COCHCl.sub.2     H                                        ##STR224##                                                                              CH.sub.3 CH.sub.3                                                                       COCHCl.sub.2     H                                        ##STR225##                                                                              Cyclohex- ane                                                                           COCHCl.sub.2     H                                        ##STR226##                                                                              Cyclohex- ene                                                                           COCHCl.sub.2     H                                        ##STR227##                                                                              Methylcy- clohexene                                                                     COCHCl.sub.2     H                                       C(CH.sub.3).sub.3                                                                        CH.sub.3 CH.sub.3                                                                       COCH.sub.3       H                                       C(CH.sub.3).sub.3                                                                        Cyclohex- COCH.sub.3       H                                                  ane                                                                C(CH.sub.3).sub.3                                                                        Cyclohex- COCH.sub.3       H                                                  ene                                                                C(CH.sub.3).sub.3                                                                        Methylcy- COCH.sub.3       H                                                  clohexene                                                          C(CH.sub.3).sub.3                                                                        CH.sub.3 CH.sub.3                                                                       CONHCH.sub.3     H                                       C(CH.sub.3).sub.3                                                                        Cyclohex- CONHCH.sub.3     H                                                  ane                                                                C(CH.sub.3).sub.3                                                                        Cyclohex- CONHCH.sub.3     H                                                  ene                                                                C(CH.sub.3).sub.3                                                                        Methylcy- CONHCH.sub.3     H                                                  clohexene                                                          C(CH.sub.3).sub.3                                                                        CH.sub.3 CH.sub.3                                                                        ##STR228##      H                                       C(CH.sub.3).sub.3                                                                        Cyclohex- ane                                                                            ##STR229##      H                                       C(CH.sub.3).sub.3                                                                        Cyclohex- ene                                                                            ##STR230##      H                                       C(CH.sub.3).sub.3                                                                        Methylcy- clohexene                                                                      ##STR231##      H                                       C(CH.sub.3).sub.3                                                                        CH.sub.3 CH.sub.3                                                                        ##STR232##      H                                       C(CH.sub.3).sub.3                                                                        Cyclohex- ane                                                                            ##STR233##      H                                       C(CH.sub.3).sub.3                                                                        Cyclohex- ane                                                                            ##STR234##      H                                       C(CH.sub.3).sub.3                                                                        Methylcy- clohexene                                                                      ##STR235##      H                                       C(CH.sub.3).sub.3                                                                        CH.sub.3 CH.sub.3                                                                       COCHCl.sub.2     H                                       C(CH.sub.3).sub.3                                                                        Cyclohex- COCHCl.sub.2     H                                                  ane                                                                C(CH.sub.3).sub.3                                                                        Cyclohex- COCHCl.sub.2     H                                                  ene                                                                C(CH.sub.3).sub.3                                                                        Methylcy- COCHCl.sub.2     H                                                  clohexene                                                          ______________________________________                                    

Other preferred compounds according to the invention are the additionproducts of acids and those 1-vinyltriazole derivatives of the formula(I) in which R¹, R², R³ and X have the meanings which have already beenmentioned as preferred therefor.

Preferred acids which can be added on include hydrogen halide acids (forexample hydrobromic acid and, in particular, hydrochloric acid),phosphoric acid, nitric acid, sulphuric acid, monofunctional andbifunctional carboxylic acids and hydroxycarboxylic acids (for exampleacetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid,citric acid, salicylic acid, sorbic acid and lactic acid) and sulphonicacids (for example p-toluenesulphonic acid and1,5-naphthalenedisulphonic acid).

Further preferred compounds according to the invention are additionproducts of salts of metals of main groups II to IV and of sub-groups Iand II and IV to VIII and those 1-vinyltriazole derivatives of theformula (I) in which R¹, R², R³ and X have the meanings which havealready been mentioned as preferred therefor. Salts of copper, zinc,manganese, magnesium, tin, iron and nickel are particularly preferred.Possible anions of these salts are those which are derived from acidswhich lead to physiologically acceptable addition products. Such acidswhich are particularly preferred in this connection are the hydrogenhalide acids (for example hydrochloric acid and hydrobromic acid),phosphoric acid, nitric acid and sulphuric acid.

If, for example, pinacolyl-1,2,4-triazole and cyclohexanecarbaldehydeare used as starting materials, the course of the reaction in processvariant (a) can be represented by the following equation: ##STR236##

If 1-cyclohexyl-4,4-dimethyl-2-(1,2,4-triazol-1-yl)pent-1-en-3-one andsodium borohydride are used as starting materials, the course of thereaction in process variant (b)(α) can be represented by the followingequation: ##STR237##

If 1-cyclohexyl-4,4-dimethyl-2-(1,2,4-triazol-1-yl)pent-1-en-3-one andmethyl-magnesium bromide are used as starting materials, the course ofthe reaction in proces variant (b)(β) can be represented by thefollowing equation: ##STR238##

If 1-cyclohexyl-4,4-dimethyl-1-(1,2,4-triazol-1yl)pent-1-en-3-ol andethyl bromide are used as starting materials and sodium hydride is usedas the base, the course of the reaction in process variant (c) can berepresented by the following equation: ##STR239##

If 1-cyclohexyl-4,4-dimethyl-2-(1,2,4-triazol-1-yl)pent-1-en-3-ol andacetyl chloride are used as starting materials and sodium hydride isused as the base, the course of the reaction in process variant (c) canbe represented by the following equation: ##STR240##

If 1-cyclohexyl-4,4-dimethyl-2-(1,2,4-triazol-1-yl)pent-1-en-3-ol andacetic anhydride are used as starting materials, the course of thereaction in process variant (d) can be represented by the followingequation: ##STR241##

If 1-cyclohexyl-4,4-dimethyl-2-(1,2,4-triazol-1-yl)pent-1-en-3-ol andphenyl isocyanate are used as starting materials, the course of thereaction in process variant (e) can be represented by the followingequation: ##STR242##

The formula (II) provides a general definition of the triazole-ketonesrequired as starting materials in carrying out process variant (a). Inthis formula, R¹ preferably has those meanings which have already beenmentioned as preferred in connection with the description of thesubstances of the formula (I).

Most of the triazole-ketones of the formula (II) are known (see DE-OS(German Published Specification) No. 2,431,407, DE-OS (German PublishedSpecification) No. 2,610,022 and DE-OS (German Published Specification)No. 2,638,470). The compounds of the formula (II) which have nothitherto been described in the literature can be prepared by customarymethods. They are obtained by reacting the corresponding halo-ketoneswith 1,2,4-triazole in the presence of an acid-binding agent. Thecompounds of the following table may be mentioned as examples:##STR243##

    __________________________________________________________________________    R.sup.1        R.sup.1          R.sup.1                                       __________________________________________________________________________    C(CH.sub.3).sub.3                                                                            CH(CH.sub.3).sub.2                                                                             CH.sub.3                                                      ##STR244##                                                                                     ##STR245##                                    ##STR246##                                                                                   ##STR247##                                                                                     ##STR248##                                    ##STR249##                                                                                   ##STR250##                                                                                     ##STR251##                                    ##STR252##                                                                                   ##STR253##                                                                                     ##STR254##                                    ##STR255##                                                                                   ##STR256##                                                                                     ##STR257##                                    ##STR258##                                                                                   ##STR259##                                                                                     ##STR260##                                    ##STR261##                                                                                   ##STR262##                                                                                     ##STR263##                                   __________________________________________________________________________

The formula (III) provides a general definition of the aldehydes also tobe used as starting materials for process variant (a). In this formula,R² and R³ preferably have those meanings which have already beenmentioned as preferred in connection with the description of thesubstances of the formula (I).

The aldehydes of the formula (III) are generally known compounds oforganic chemistry. The following compounds may be mentioned as examples:##STR264##

The formula (Ia) provides a general definition of the compounds to beused as starting materials for process variants (b)(α) and (b)(β). Inthis formula, R¹, R² and R³ preferably have those meanings which havealready been mentioned as preferred in connection with the descriptionof the substances of the formula (I).

Compounds of the formula (Ia) in which R¹ represents optionallysubstituted alkyl or cycloalkyl are according to the invention, whereassome of those in which R¹ represents optionally substituted aryl areknown (see DE-OS (German Published Specification) No. 2,645,617).

The complex hydrides required as reaction components for process variant(b)(α) are generally known compounds of organic chemistry. Preferredexamples which may be mentioned are sodium borohydride and lithiumalanate.

The formula (IV) provides a general definition of the Grignard compoundsalso to be used as starting substances for process variant (b)(β). Inthis formula, R⁶ preferably represents alkyl with 1 to 4 carbon atoms oraralkyl with 1 to 2 carbon atoms in the alkyl part and 6 to 10 carbonatoms in the aryl part, benzyl being mentioned as an example, which isoptionally substituted by halogen or alkyl with 1 to 4 carbon atoms. Halpreferably represents chlorine, bromine or iodine.

The Grignard compounds of the formula (IV) are generally known compoundsof organic chemistry. Examples which may be mentioned aremethyl-magnesium bromide, ethyl-magnesium bromide, isopropyl-magnesiumbromide and benzyl-magnesium bromide.

The formula (Ib) provides a general definition of the 1-vinyltriazolederivatives to be used as starting materials for process variants (c),(d) and (e). In this formula, R¹, R², R³ and R⁵ preferably have thosemeanings which have already been mentioned as preferred in connectionwith the description of the substances of the formula (I).

The formula (V) provides a general definition of the halides also to beused as starting materials for process variant (c). In this formula, R⁷preferably represents straight-chain or branched alkyl with 1 to 4carbon atoms or aralkyl with 1 to 2 carbon atoms in the alkyl part and 6to 10 carbon atoms in the aryl part, such as benzyl or naphthylmethyl,which is optionally monosubstituted or polysubstituted by identical ordifferent substituents, preferred substituents being halogen,, alkylwith 1 to 4 carbon atoms, haloalkyl with up to 2 carbon atoms and up to3 identical or different halogen atoms, preferred halogen atoms beingfluorine and chlorine, and phenyl and phenoxy, optionally substituted byhalogen. R⁷ furthermore preferably represents the acyl radical --CO--R¹⁰or the carbamoyl radical --CO--NR¹¹ R¹², wherein R¹⁰, R¹¹ and R¹²preferably have those meanings which have already been mentioned aspreferred for these radicals in connection with the description of thesubstances according to the invention. Hal' in formula (V) preferablyrepresents fluorine, chlorine or bromine.

The halides of the formula (V) are generally known compounds of organicchemistry.

The formula (VI) provides a general definition of the acid anhydridesalso to be used as starting substances for process variant (d). In thisformula, R⁸ preferably represents the acyl radical of the formula--CO--R¹⁰, wherein R¹⁰ preferably has those meanings which have alreadybeen mentioned as preferred for this radical in connection with thedescription of the substances according to the invention.

The acid anhydrides of the formula (VI) are generally known compounds oforganic chemistry.

The formula (VII) provides a general definition of the isocyanates alsoto be used as starting substances for process variant (e). In thisformula, R⁹ preferably represents alkyl with 1 to 8 carbon atoms,haloalkyl with up to 4 carbon atoms and up to 5 identical or differenthalogen atoms, such as, in particular, fluorine and chlorine atoms, arylwith 6 to 10 carbon atoms, such as phenyl and naphthyl, which isoptionally monosubstituted or polysubstituted by identical or differentsubstituents, preferred substituents being halogen, alkyl with 1 to 4carbon atoms and haloalkyl with up to 2 carbon atoms and up to 5identical or different halogen atoms, such as, in particular, fluorineand chlorine atoms, or preferably represents haloalkyl-mercapto with 1to 2 carbon atoms and up to 5 halogen atoms, such as, in particular,fluorine and chlorine atoms.

The isocyanates of the formula (VII) are generally known compounds oforganic chemistry.

Preferred solvents for process variant (a) of the invention are inertorganic solvents. These include, as preferences, alcohols, such asmethanol and ethanol; ethers, such as tetrahydrofuran and dioxan;aliphatic and cycloaliphatic hydrocarbons, such as hexane andcyclohexane; aromatic hydrocarbons, such as benzene, toluene and cumene;and halogenated aliphatic and aromatic hydrocarbons, such as methylenechloride, carbon tetrachloride, chloroform, chlorobenzene anddichlorobenzene.

Process variant (a) is carried out in the presence of a catalyst. Any ofthe acid and, especially, basic catalysts, and buffer mixtures thereof,which can customarily be used can be employed. These catalysts include,as preferences, Lewis acids, for example boron trifluoride, borontrichloride, tin tetrachloride or titanium tetrachloride; organic bases,such as pyridine and piperidine; and, especially, piperidine acetate.

The reaction temperatures can be varied within a substantial range incarrying out process variant (a). In general, the reaction is carriedout at from 20° to 160° C., preferably at the boiling point of theparticular solvent.

In carrying out process variant (a), 1 to 1.5 moles of aldehyde of theformula (III) and a catalytic amount to 0.2 mole of catalyst areemployed per mole of triazoleketone of the formula (II). To isolate thecompounds of the formula (I), the two reaction products, which areisomeric with regard to the position of the double bond, are separatedby customary methods, for example by salt formation (see the preparativeexamples) or by chromatography. Unambiguous allocation of structure iseffected on the basis of spectroscopic data, in particular the NMR data.

Preferred solvents for process variant (b)(α) are polar organicsolvents. These include, as preferences, alcohols, such as methanol,ethanol, isopropanol or butanol; and ethers, such as diethyl ether ortetrahydrofuran.

The reaction temperatures can be varied within a substantial range incarrying out process variant (b)(α). In general, the reaction is carriedout at from 0° to 30° C., preferably at from 0° to 20 °C.

Equivalent amounts of starting materials are preferably used forcarrying out process variant (b)(α). To isolate the compound of theformula (I), the reaction mixture is taken up in dilute hydrochloricacid and extracted with an organic solvent. Further working up iseffected in the customary manner.

Preferred solvents for process variant (b)(β) are anhydrous ethers, suchas diethyl ether, dibutyl ether or tetrahydrofuran.

The reaction temperatures can be varied within a substantial range incarrying out process variant (b)(β). In general, the reaction is carriedout at from 0° to 80° C., preferably from 30° to 60° C.

Equivalent amounts of starting substances are preferably used forcarrying out process variant (b)(β). Isolation of the compound of theformula (I) is effected in a customary and generally known manner.

Preferred solvents for process variant (c) are inert organic solvents.These include, as preferences, ethers, such as diethyl ether and dioxan;aromatic hydrocarbons, such as toluene and benzene (and in some cases,also chlorinated hydrocarbons, such as chloroform, methylene chloride orcarbon tetrachoride); ketones, such as acetone or methyl ethyl ketone;and nitriles, such as acetonitrile. For reasons of simplicity, an acidhalide employed can also be used as the solvent, whereupon anappropriate excess becomes necessary.

The reaction temperatures can be varied within a substantial range incarrying out process variant (c). In general, the reaction is carriedout at from 20° to 150° C., preferably from 20° to 100° C., or at theboiling point of the particular solvent.

If appropriate, process variant (c) can be carried out in the presenceof a strong base. Preferred strong bases include alkali metal hydrides,alkali metal amides and alkali metal alcoholates, for example sodiumhydride, sodium amide and potassium tert.-butylate.

If appropriate, process variant (c) can be carried out in the presenceof an acid-binding agent (hydrogen halide acceptor). Suitableacid-binding agents include organic bases, preferably tertiary amines,for example triethylamine; and furthermore inorganic bases, for examplealkali metal hydroxides and alkali metal carbonates.

In carrying out process variant (c), 1 to 3 moles of halide of theformula (V) are preferably employed per mole of the compound of theformula (Ib). To isolate the end product, the reaction mixture is freedfrom solvent, and water and an organic solvent are added to the residue.The organic phase is separated off and worked up in the customarymanner.

In a preferred embodiment, a procedure is appropriately followed inwhich a compound of the formula (Ib) is used as the starting material,this compound is converted into the alkenolate in a suitable inertorganic solvent by means of an alkali metal hydride or alkali metalamide and the alkenolate is reacted immediately, without isolation, witha halide of the formula (V), the compound of the formula (I) beingobtained in one operation with elimination of an alkali metal halide.

According to another preferred embodiment, the reaction of a halide ofthe formula (V), in which R⁷ represents alkyl or optionally substitutedaralkyl, in the above-mentioned preferred embodiment is carried out in atwo-phase system, for example aqueous sodium hydroxide solution orpotassium hydroxide solution/toluene or methylene chloride, with theaddition of 0.01-1 mole of a phase transfer catalyst, for example anammonium or phosphonium compound, for examplebenzyl-dodecyl-dimethyl-ammonium chloride (Zephirol) ortriethyl-benzyl-ammonium chloride.

Preferred solvents for process variant (d) are inert organic solvents.These include, as preferences, the solvents listed in the case ofprocess variant (c) and the particular acid anhydrides of the formula(VI) used.

Preferred catalysts which can be used in process variant (d) are any ofthe customary acid and basic catalysts, for example sulphuric acid,hydrogen chloride, hydrogen bromide, boron trifluoride, zinc chloride,sodium acetate, sodium benzoate, sodium carbonate, calcium oxide,magnesium oxide, pyridine and triethylamine.

The reaction temperatures can be varied within a substantial range incarrying out process variant (d). In general, the reaction is carriedout at from 20° to 150° C., preferably from 50° to 120° C.

Equivalent amounts of starting materials are preferably used in carryingout process variant (d). For reasons of simplicity, the acid anhydrideof the formula (VI) employed can also be used as the solvent, whereuponan appropriate excess becomes necessary. Isolation of the compound ofthe formula (I) is effected in the customary manner.

Preferred solvents for process variant (e) are inert organic solvents.These include, as preferences, the solvents listed in the case ofprocess variant (c).

Preferred catalysts which can be used in process variant (e) aretertiary bases, such as triethylamine and pyridine, or organo-tincompounds, such as dibutyl-tin dilaurate and tributyl-tin laurate.

The reaction temperatures can be varied within a substantial range incarrying out process variant (e). In general, the reaction is carriedout at from 0° to 100° C., preferably from 20° to 40° C.

Equivalent amounts of starting substances are preferably used incarrying out process variant (e). To isolate the compound of the formula(I), the solvent is distilled off and the residue is worked up bycustomary methods.

The compounds of the formula (I) can be converted into acid additionsalts or metal salt complexes.

The following acids can preferably be used to prepare physiologicallyacceptable acid addition salts of the compounds of the formula (I): thehydrogen halide acids (for example hydrobromic acid and, especially,hydrochloric acid), phosphoric acid, nitric acid, sulphuric acid,monofunctional and bifunctional carboxylic acids and hydroxycarboxylicacids (for example acetic acid, maleic acid, succinic acid, fumaricacid, tartaric acid, citric acid, salicylic acid, sorbic acid and lacticacid) and sulphonic acids (for example p-toluenesulphonic acid and1,5-naphthalene-disulphonic acid).

The acid addition salts of the compounds of the formula (I) can beobtained in a simple manner by customary salt formation methods, forexample by dissolving a compound of the formula (I) in a suitable inertsolvent and adding the acid, for example hydrochloric acid, and they canbe isolated in a known manner, for example by filtration, and isappropriate purified by washing with an inert organic solvent.

Salts of metals of main groups II to IV and of sub-groups I and II andIV to VIII can be used to prepare metal salt complexes of the compoundsof the formula (I), examples of metals which may be mentioned beingcopper, zinc, manganese, magnesium, tin, iron and nickel.

Possible anions of the salts are preferably those which are derived fromthe following acids: hydrogen halide acids (for example hydrochloricacid and hydrobromic acid), phosphoric acid, nitric acid and sulphuricacid.

The metal complexes of compounds of the formula (I) can be obtained in asimple manner by customary processes, for example by dissolving themetal salt in alcohol, for example ethanol, and adding the solution tothe compound of the formula (I). The metal salt complexes can bepurified in a known manner, for example by filtration, isolation and ifappropriate by recrystallization.

The compounds according to the present invention engage in themetabolism of plants and can therefore be employed as growth regulators.

Experience to date of the mode of action of plant growth regulators hasshown that an active compound can exert one or several different actionson plants. The actions of the compounds depend essentially on the pointin time at which they are used, relative to the stage of development ofthe seed or of the plant, and on the amounts of active compound appliedto the plants or their environment and the way in which the compoundsare applied. In every case, growth regulators are intended positively toinfluence the crop plants in the desired manner.

Plant growth-regulating compounds can be employed, for example, toinhibit vegetative plant growth. Such inhibition of growth is inter aliaof economic interest in the case of grasses since, by repressing thegrowth of grass, it is possible, for example, to reduce the frequency ofcutting the grass in ornamental gardens, parks and sports grounds or atverges. The inhibition of growth of herbaceous and woody plants atverges and in the vicinity of overland pipelines or, quite generally, inareas in which heavy growth is undesired, is also of importance.

The use of growth regulators to inhibit the growth in length of cerealsis also important, since by shortening the stem of the danger of lodgingof the plants before harvesting is reduced or completely eliminated.Furthermore, growth regulators can strengthen the stem of cereals, whichcan counteract lodging.

In the case of many crop plants, inhibition of the vegetative growthpermits denser planting of the crop, so that a greater yield per area ofground can be achieved.

A further mechanism of increasing the yield by means of growthinhibitors is based on the fact that the nutrients benefit blossomingand fruit formation to a greater extent, while vegetative growth isrestricted.

Promotion of vegetative growth can also frequently be achieved withgrowth regulators. This is of great utility if it is the vegetativeparts of the plants which are harvested. Promoting the vegetative growthcan, however, also simultaneously lead to a promotion of generativegrowth, so that, for example, more fruit, or larger fruit, is formed.

Increases in yield can in some cases also be achieved by affecting theplant metabolism, without noticeable changes in vegetative growth.Growth regulators can furthermore produce a change in the composition ofthe plants so as to bring about better quality of the harvestedproducts. Thus it is possible, for example, to increase the content ofsugar in sugar beet, sugar cane, pineapples and citrus fruit or toincrease the protein content in soya or cereals.

Parthenocarpous fruit can be formed under the influence of growthregulators. Furthermore, the gender of the flowers can be influenced.

Using growth regulators it is also possible favorably to influence theproduction or the efflux of secondary plant materials. The stimulationof latex flow in rubber trees may be mentioned as an example.

During the growth of the plant, lateral branching can also be increased,by using growth regulators, through chemical breaking of the apicaldominance. There is interest in this, for example, in the case of plantpropagation by cuttings. However, it is also possible to inhibit thegrowth of side shoots, for example to prevent the formation of sideshoots in tobacco plants after decapitation and thus to promote leafgrowth.

The amount of leaf on plants can be controlled, under the influence ofgrowth regulators, so that defoliation of the plants at a desired pointin time is achieved. Such defoliation is of interest to facilitatemechanical harvesting, for example of grapes or cotton, or to lower thetranspiration at a point in time at which the plant is to betransplanted.

Premature shedding of fruit can be prevented by the use of growthregulators. However, it is also possible to promote the shedding offruit--for example in the case of table fruit--in the sense of achemical thinning out, up to a certain degree. Growth regulators canalso be used to reduce the force required to detach the fruit from cropplants at harvest time so as to permit mechanical harvesting of theplants or facilitate manual harvesting.

Using growth regulators it is furthermore possible to achieve anacceleration or retardation of ripening of the harvest product, beforeor after harvesting. This is of particular advantage since it is therebypossible to achieve optimum adaptation to market requirements.Furthermore, growth regulators can at times improve the coloration offruit. In addition, concentrating the ripening within a certain periodof time is also achievable with the aid of growth regulators. Thisprovides the preconditions for being able to carry out completemechanical or manual harvesting in only a single pass, for example inthe case of tobacco, tomatoes or coffee.

Using growth regulators it is also possible to influence the latentperiod of seeds or buds of plants, that is to say the endogenic annualrhythm, so that the plants, such as, for example, pineapple ordecorative plants in nurseries, germinate, shoot or blossom at a time atwhich they normally show no readiness to do so.

Using growth regulators it is also possible to achieve a delay in theshooting of buds or the germination of seeds, for example to avoiddamage by late frosts in regions where frost is a hazard.

Growth regulators can also produce halophilism in crop plants. Thisprovides the preconditions for being able to cultivate plants on soilscontaining salt.

Using growth regulators, it is also possible to induce frost resistanceand drought resistance in plants.

The preferred time of application of the growth regulators depends onthe climatic and vegetative circumstances.

The foregoing description should not be taken as implying that each ofthe compounds can exhibit all of the described effects on plants. Theeffect exhibited by a compound in any particular set of circumstancesmust be determined empirically.

The active compounds according to the invention also exhibit a powerfulmicrobicidal action and can be employed in practice for combatingundesired micro-organisms. The active compounds are suitable for use asplant protection agents.

Fungicidal agents in plant protection are employed for combatingPlasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes.

The good toleration, by plants, of the active compounds, at theconcentrations required for combating plant diseases, permits treatmentof above-ground parts of plants, of vegetative propagation stock andseeds, and of the soil.

As plant protection agents, the active compounds which can be usedaccording to the invention can be employed with particularly goodsuccess for combating those fungi which cause powdery mildew diseases,especially for combating Erysiphe species, for example the powderymildew of barley or cereal causative organism (Erysiphe graminis). Itshould be particularly emphasized that the active compounds according tothe invention not only develop a protective action, but also have asystemic action. Thus, it is possible to protect plants against fungalattack when the active compound is fed to the above-ground parts of theplants via the soil and the root or via the seed.

The active compounds can be converted into the customary formulations,such as solutions, emulsions, powders, suspensions, powders, dustingagents, foams, pastes, soluble powders, granules, aerosols,suspension-emulsion concentrates, seed-treatment powders, natural andsynthetic materials impregnated with active compound, very fine capsulesin polymeric substances, coating compositions for use on seed, andformulations used with burning equipment, such as fumigating cartridges,fumigating cans and fumigating coils, as well as ULV cold mist and warmmist formulations.

These formulations may be produced in known manner, for example bymixing the active compounds with extenders, that is to say liquid orliquefied gaseous or solid diluents or carriers, optionally with the useof surface-active agents, that is to say emulsifying agents and/ordispersing agents and/or foam-forming agents. In the case of the use ofwater as an extender, organic solvents can, for example, also be used asauxiliary solvents.

As liquid diluents or carriers, especially solvents, there are suitablein the main, aromatic hydrocarbons, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic or chlorinated aliphatichydrocarbons, such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane orparaffins, for example mineral oil fractions, alcohols, such as butanolor glycol as well as their ethers and esters, ketones, such as acetone,methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, orstrongly polar solvents, such as dimethylformamide anddimethylsulphoxide, as well as water.

By liquefied gaseous diluents or carriers are meant liquids which wouldbe gaseous at normal temperature and under normal pressure, for exampleaerosol propellants, such as halogenated hydrocarbons as well as butane,propane, nitrogen and carbon dioxide.

As solid carriers there may be used ground natural minerals, such askaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite ordiatomaceous earth, and ground synthetic minerals, such ashighly-dispersed silicic acid, alumina and silicates. As solid carriersfor granules there may be used crushed and fractionated natural rockssuch as calcite, marble, pumice, sepiolite and dolomite, as well assynthetic granules of inorganic and organic meals, and granules oforganic material such as sawdust, coconut shells, maize cobs and tobaccostalks.

As emulsifying and/or foam-forming agents there may be used non-ionicand anionic emulsifiers, such as polyoxyethylene-fatty acid esters,polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycolethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well asalbumin hydrolysis products. Dispersing agents include, for example,lignin sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, can be used in theformulations.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs or metal phthalocyaninedyestuffs, and trace nutrients, such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain from 0.1 to 95 percent by weight ofactive compound, preferably from 0.5 to 90 percent by weight.

The active compounds according to the invention can be present in theformulations, or in the various use forms, as a mixture with otheractive compounds, such as fungicides, bactericides, insecticides,acaricides, nematicides, herbicides, bird repellants, growth factors,plant nutrients and agents for improving soil structure, as well asother plant growth regulators.

The active compounds can be used as such or in the form of theirformulations or the use forms prepared therefrom by further dilution,such as ready-to-use solutions, emulsions, suspensions, powders, pastesand granules. They are used in the customary manner, for example bywatering, immersion, spraying, atomizing, misting, vaporizing,injecting, forming a slurry, brushing on, dusting, scattering, drydressing, moist dressing, wet dressing, slurry dressing or encrusting.Furthermore, it is possible to apply the active compounds in accordancewith the ultra-low volume process or to inject the active compoundpreparation or the active compound itself into the soil. It is alsopossible to treat the seeds of plants.

When the compounds according to the invention are used as plant growthregulators, the amounts used can be varied within a substantial range.In general, 0.01 to 50 kg, preferably 0.05 to 10 kg, of the activecompound are employed per hectare of soil surface.

When the substances according to the invention are used as fungicides,the amount used can also be varied within a substantial range, dependingon the nature of the application. Thus, especially in the treatment ofparts of plants, the active compound concentrations in the use forms arein general between 1 and 0.0001% by weight, especially between 0.5 and0.001%. In the treatment of seed, amounts of active compound of 0.001 to50 g, especially 0.01 to 10 g, are generally required per kilogram ofseed. For the treatment of soil, active compound concentrations of0.00001 to 0.01% by weight, especially 0.0001 to 0.02%, are generallyrequired at the place of action.

The present invention also provides plant-growth regulating orfungicidal compositions containing as active ingredient a compound ofthe present invention in admixture with a solid or liquefied gaseousdiluent or carrier or in admixture with a liquid diluent or carriercontaining a surface-active agent.

The present invention also provides a method of combating fungi whichcomprises applying to the fungi, or to a habitat thereof, a compound ofthe present invention alone or in the form of a composition containingas active ingredient a compound of the present invention in admixturewith a diluent or carrier.

The present invention also provides a method of regulating the growth ofplants which comprises applying to the plants, or to a habitat thereof,a compound of the present invention alone or in the form of acomposition containing an active ingredient a compound of the presentinvention in admixture with a diluent or carrier.

The present invention further provides crops protected from damage byfungi by being grown in areas in which immediately prior to and/orduring the time of the growing a compound of the present invention wasapplied alone or in admixture with a diluent or carrier.

The present invention further provides plants, the growth of which hasbeen regulated by their being grown in areas in which immediately priorto and/or during the time of the growing a compound of the presentinvention was applied alone or in admixture with a diluent or carrier.

It will be seen that the usual methods of providing a harvested crop maybe improved by the present invention.

The plant-growth regulating and fungicidal activity of the compounds ofthis invention is illustrated by the following biotest Examples.

In these Examples, the compounds according to the present invention areeach identified by the number (given in brackets) of the correspondingpreparative Example, which will be found later in this specification.

The known comparison compounds are identified as follows: ##STR265##

EXAMPLE A

Formation of ethylene

Solvent: 30 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of polyoxyethylene sorbitan monolaurate

To produce a suitable preparation of active compound, 1 part by weightof active compound was mixed with the stated amounts of solvent andemulsifier and the mixture was made up to the desired concentration withwater.

Pieces of leaf of identical size were punched from soya bean leaves.These were introduced into vessels which could be closed air-tight,together with 1 ml of the preparation of active compound or controlsolution. After 24 hours the ethylene which had collected in the vesselswas determined by customary methods of detection. The evolution ofethylene from the pieces of leaf treated with the preparations of activecompound was compared with the evolution of ethylene from the controls.

Compared with the control, active compound (3) caused a greatlyincreased evolution of ethylene.

EXAMPLE B

Inhibition of growth of barley

Solvent: 30 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of polyoxyethylene sorbitan monolaurate

To produce a suitable preparation of active compound, 1 part by weightof active compound was mixed with the stated amounts of solvent andemulsifier and the mixture was made up to the desired concentration withwater.

Barley plants were grown in a greenhouse to the 2-leaf stage. In thisstage, the plants were sprayed with the preparations of active compounduntil dripping wet. After 3 weeks, the additional growth was measured onall plants and the inhibition of growth in percent of the additionalgrowth of the control plants was calculated. 100% inhibition of growthmeant that growth had stopped and 0% denoted a growth corresponding tothat of the control plants.

In this test, active compounds (2), (3) and (12) exhibited a betterinhibition of growth than substance (A) which is known from the priorart.

EXAMPLE C

Influence on growth of sugar-beet

Solvent: 30 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of polyoxyethylene sorbitan monolaurate

To produce a suitable preparation of active compound, 1 part by weightof active compound was mixed with the stated amounts of solvent andemulsifier and the mixture was made up to the desired concentration withwater.

Sugar beet was grown in a greenhouse until formation of the cotyledonswas complete. In this stage, the plants were sprayed with thepreparations of active compound until dripping wet. After 14 days, theadditional growth of the plants was measured and the influence on growthin percent of the additional growth of the control plants wascalculated. 0% influence on growth denoted a growth which correspondedto that of the control plants. Negative values characterized aninhibition of growth in comparison to the control plants, whereaspositive values characterized a promotion of growth in comparison to thecontrol plants.

In this test, active compounds (2), (3), (4), (12), (14) and (16)influenced growth better than substance (B) which is known from theprior art.

EXAMPLE D

Inhibition of growth of soya beans

Solvent: 30 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of polyoxyethylene sorbitan monolaurate

To produce a suitable preparation of active compound, 1 part by weightof active compound was mixed with the stated amounts of solvent andemulsifier and the mixture was made up to the desired concentration withwater.

Soya bean plants were grown in a greenhouse until the first secondaryleaf had unfolded completely. In this stage, the plants were sprayedwith the preparations of active compound until dripping wet. After 3weeks, the additional growth was measured on all the plants and theinhibition of growth in percent of the additional growth of the controlplants was calculated. 100% inhibition of growth meant that growth hadstopped and 0% denoted a growth corresponding to that of the controlplants.

In this test, active compounds (2), (3), (12), (13), (14) and (16)exhibited a better inhibition of growth than substance (B) which isknown from the prior art.

EXAMPLE E

Inhibition of growth of cotton

Solvent: 30 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of polyoxyethylene sorbitan monolaurate

To produce a suitable preparation of active compound, 1 part by weightof active compound was mixed with the stated amounts of solvent andemulsifier and the mixture was made up to the desired concentration withwater.

Cotton plants were grown in a greenhouse until the 5th secondary leafhad unfolded completely. In this stage, the plants were sprayed with thepreparations of active compound until dripping wet. After 3 weeks, theadditional growth of the plants was measured and the inhibition ofgrowth in percent of the additional growth of the control plants wascalculated. 100% inhibition of growth meant that growth had stopped and0% denoted a growth corresponding to that of the control plants.

In this test, compared with the control, active compounds (2), (3), (4)and (12) exhibited a powerful inhibition of growth.

EXAMPLE F

Shoot treatment test/powdery mildew of cereals (leaf-destructivemycosis)/protective

To produce a suitable preparation of active compound, 0.25 part byweight of active compound was taken up in 25 parts by weight ofdimethylformamide and 0.06 part by weight of alkylaryl polyglycol ether;975 parts by weight of water were then added. The concentrate wasdiluted with water to the desired final concentration of the sprayliquor.

To test for protective activity, single-leaved young barley plants ofthe Amsel variety were sprayed with the preparation of active compounduntil dew-moist. After drying, the barley plants were dusted with sporesof Erysiphe graminis var. hordei.

After 6 days' dwell time of the plants at a temperature of 21-22 deg. Cand 80-90% atmospheric humidity the occurrence of mildew pustules on theplants was evaluated. The degree of infection was expressed as apercentage of the infection of the untreated control plants. 0% denotedno infection and 100% denoted the same degree of infection as in thecase of the untreated control. The active compound was the more active,the lower was the degree of mildew infection.

In this test, for example, the following compounds exhibited a very goodaction, which was superior to that of the compounds (C), (D) and (E)known from the prior art: compounds (2), (3), (16), (4), (11) and (12).

EXAMPLE G

Powdery mildew of barley (Erysiphe graminis var. hordei) (fungal diseaseof cereal shoots)/systemic

The active compound was used as a pulverulent seed treatment agent. Thiswas prepared by extending the particular active compound with a mixtureof equal parts by weight of talc and kieselguhr to give a finelypulverulent mixture of the desired concentration of active compound.

For the treatment seed, barley seed was shaken with the extended activecompound in a closed glass bottle. The seed was sown at the rate of 3×12grains in flowerpots, 2 cm deep in a mixture of one part by volume ofFruhstorfer standard soil and one part by volume of quartz sand. Thegermination and emergence took place under favourable conditions in agreenhouse. 7 days after sowing, when the barley plants had developedtheir first leaf, they were dusted with fresh spores of Erysiphegraminis var. hordei and grown on at 21-22 deg. C and 80-90% relativeatmospheric humidity and 16 hours' exposure to light. The typical mildewpustules formed on the leaves over the course of 6 days.

The degree of infection was expressed as a percentage of the infectionof the untreated control plants. Thus, 0% denoted no infection and 100%denoted the same degree of infection as in the case of the untreatedcontrol. The active compound was the more active, the lower was thedegree of mildew infection.

In this test, for example, the following compounds exhibited a very goodaction which was superior to that of the compounds (F), (G) and (H)known from the prior art: compounds (2), (3), (4), (11) and (12).

EXAMPLE H

Mycelium growth test

Nutrient medium used:

20 parts by weight of agar-agar

200 parts by weight of potato decoction

5 parts by weight of malt

15 parts by weight of dextrose

5 parts by weight of peptone

2 parts by weight of disodium hydrogen phosphate

0.3 part by weight of calcium nitrate

Ratio of solvent mixture to nutrient medium:

2 parts by weight of solvent mixture

100 parts by weight of agar nutrient medium

Composition of the solvent mixture:

0.19 part by weight of acetone or dimethylformamide

0.01 part by weight of emulsifier (alkylaryl polyglycol ether)

1.80 parts by weight of water

The amount of active compound required for the desired active compoundconcentration in the nutrient medium was mixed with the stated amount ofsolvent mixture. The concentrate was thoroughly mixed, in the statedproportion, with the liquid nutrient medium (which had been cooled to 42deg. C.) and was then poured into Petri dishes of 9 cm diameter. Controlplates to which the preparation had not been added were also set up.

When the nutrient medium had cooled and solidified, the plates wereinoculated with the species of organisms state hereinbelow and incubatedat about 21 deg. C.

Evaluation was carried out after 4-10 days, dependent upon the speed ofgrowth of the organisms. When evaluation was carried out the radialgrowth of the organism on the treated nutrient media was compared withthe growth on the control nutrient medium. In the evaluation of theorganism growth, the following characteristic values were used:

    ______________________________________                                        1         no growth                                                           up to 3  very strong inhibition of growth                                     up to 5  medium inhibition of growth                                          up to 7  slight inhibition of growth                                          9        growth equal to that of untreated control.                           ______________________________________                                    

As test organisms, the following fungi were employed:

In this test, for example, the following compounds exhibited a very goodaction which was superior to that of the compound (I) known from theprior art: compounds (2) and (3).

EXAMPLE I

Inhibition of growth of rice

Solvent: 30 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of polyoxyethylene sorbitan monolaurate

To produce a suitable preparation of active compound, 1 part by weightof active compound was mixed with the stated amounts of solvent andemulsifier and the mixture was made up to the desired concentration withwater.

Rice plants were grown in a green-house to the 2-leaf stage in 10×10×10cm pots filled with earth. In this stage, the plants were sprayed withthe preparations of active compound until dripping wet. After 10 days,the additional growth was measured on all plants and the inhibition ofgrowth in percent of the additional growth of the control plants wascalculated. 100% inhibition of growth meant that growth had stopped and0% denoted a growth corresponding to that of the control plants.

In this test, active compound (2) exhibited a strong growth inhibitingactivity.

EXAMPLE J

Inhibition of growth of water-rice (var. Nihonbare)

5 parts of active compound were mixed in a mixer with 2.5 parts ofNewkalgen CP-50⁺), 30 parts of Bentonit and 62.5 parts of talkum. Then20 parts of water were added. The pasty material was pressed throughwholes of a diameter of 0.5 mm and then was dried. There was obtained agranulate having a corn size of a diameter of 0.5 mm and a length of 0.7mm.

Ten days old rice plants were planted in containers having a size of25×20×10 cm, in which containers water is dammed up above the soil.After 10 days, the preparation of active compound was applied to thewater. After an additional period of 14 days, the hight of the plantswas measured. ##STR266##

R=Ethylen or propylen in a ratio of 9:1

In this test, the active compound (2) exhibited a very strong growthinhibiting activity.

PREPARATIVE EXAMPLES EXAMPLE 1 ##STR267##

Process variant (a)

83.5 g (0.5 mol) of pinacolyl-1,2,4-triazole, 60 g (0.54 mol) ofcyclohexanealdehyde, 4.2 g (0.05 mol) of piperidine and 6 g (0.1 mol) ofglacial acetic acid in 300 ml of toluene were heated under reflux, usinga water separator, until no further water passed over. After cooling thereaction solution, it was washed with saturated sodium chloridesolution, the organic phase was dried over sodium sulphate and filteredand the filtrate was concentrated. The residue was taken up in 500 ml ofacetone, and a filtered solution of 90 g (0.25 mol) ofnaphthalene-1,5-disulphonic acid in 500 ml of acetone was added, whilststirring.

The precipitate which initially separated out was filtered off, thefiltrate was concentrated further and the resulting colourlesscrystalline residue was taken up in 500 ml of methylene chloride.Thereafter, half-concentrated sodium carbonate solution was added untilthe mixture had an alkaline reaction. The organic phase was separatedoff, dried and filtered and the filtrate was concentrated. The oilyresidue was taken up in petroleum ether and the mixture was left tocrystallise. 64 g (49% of theory) of1-cyclohexyl-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-pent-1-en-3-one ofmelting point 98° C. were obtained.

Preparation of the starting material ##STR268##

138 g (2 mol) of 1,2,4-triazole were added in portions to 276.4 g (2mol) of ground potassium carbonate and 269.2 g (2 mol) ofα-chloropinacolin in 500 ml of acetone at room temperature, the internaltemperature rising to the boiling point. The reaction mixture wasstirred under reflux for 5 hours and then cooled to room temperature. Itwas filtered and the filtrate was concentrated by distilling off thesolvent in vacuo. After adding benzene, the oily residue crystallized.240.8 g (72% of theory) of3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-one of melting point 62°-64°C. were obtained.

EXAMPLE 2 ##STR269##

Process variant (b)(α):

26 g (0.1 mol) of1-cyclohexyl-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-pent-1-en-3-one(Example 1) were taken up in 200 ml of methanol, and 4.5 g of sodiumborohydride were added in portions, whilst stirring and cooling. Whenthe reaction had ended, the reaction mixture was adjusted to pH 6 andconcentrated. The residue was taken up in 200 ml of methylene chloride,the methylene chloride mixture was washed with saturated sodiumbicarbonate solution, dried over sodium sulphate and filtered and thefiltrate was concentrated. The residue was recrystallised from petroleumether. 14.5 g (55% of theory) of1-cyclohexyl-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-pent-1-en-3-ol ofmelting point 131° C. were obtained.

EXAMPLE 3 ##STR270##

Process variant (c)

A solution of 26.3 g (0.1 mol) of1-cyclohexyl-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-pent-1-en-3-ol (Example2) in 50 ml of dioxan was added dropwise to a suspension of 3 g of 80%strength sodium hydride in 100 ml of dioxan. When the addition hadended, the mixture was warmed to 50° C. for 1 hour. After cooling, 10.9g (0.1 mol) of ethyl bromide were added dropwise and the reactionmixture was heated under reflux overnight. After cooling, 10 ml ofmethanol were added and the mixture was concentrated in a rotaryevaporator. The residue was taken up in methylene chloride and themethylene chloride mixture was washed with water. After drying theorganic phase over sodium sulphate, it was filtered and the filtrate wasconcentrated. The residue was distilled. 11.0 g (37.8% of theory) of1-cyclohexyl-3-ethoxy-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-pent-1-ene ofboiling point 110° C./0.07 mm Hg were obtained.

EXAMPLE 4 ##STR271##

Process variant (c)

A solution of 13.15 g (0.05 mol) of1-cyclohexyl-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-pent-1-en-3-ol (Example2) in 50 ml of dioxan was added dropwise to a suspension of 1.5 g of 80%strength sodium hydride in 50 ml of dioxan. When the evolution ofhydrogen had ended, 3.9 g (0.05 mol) of acetyl chloride were addeddropwise. The mixture was heated under reflux for 4 hours. After coolingthe mixture, the solvent was distilled off in vacuo, the residue wastaken up in methylene chloride and the methylene chloride mixture wasextracted with water. The organic phase was dried over sodium sulphateand filtered and the solution was concentrated. The residue was purifiedover a column (silica gel; methanol:chloroform=1:3). 5.6 g (35.4% oftheory) of3-acetoxy-1-cyclohexyl-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-pen-1-enewere obtained as a pale yellow oil.

Process variant (d)

2 ml of pyridine were added to a solution of 13.15 g (0.05 mol) of1-cyclohexyl-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-pent-1-en-3-ol (Example2) in 100 ml of acetic anhydride. The mixture was stirred at 70° C. for4 hours. Thereafter, the reaction mixture was poured onto water andneutralised with sodium bicarbonate. The aqueous phase was extractedseveral times with ether. The combined ether phases were dried oversodium sulphate and concentrated. 11.2 g (70.8% of theory) of3-acetoxy-1-cyclohexyl-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-pent-1-enewere obtained as a pale yellow oil.

EXAMPLE 5 ##STR272##

Process variant (e)

6.5 g (0.055 mol) of phenyl isocyanate and three drops of tributyl-tinlaurate, as the catalyst, were added to a solution of 13.15 g (0.05 mol)of 1-cyclohexyl-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-pent-1-en-3-ol(Example 2) in 100 ml of ether. The mixture was stirred at roomtemperature for 5 days. After distilling off the solvent in vacuo, theresidue was recrystallised from ethyl acetate/ligroin. 4.8 g (25.1% oftheory) of1-cyclohexyl-4,4-dimethyl-3-phenylcarbamoyloxy-2-(1,2,4-triazol-1-yl)-pent-1-eneof melting point 156° C. were obtained.

The following compounds of Table 1 were obtained by procedures analogousto those described in the above Examples.

    __________________________________________________________________________     ##STR273##                                        (I)                        Ex-                                            Melting                        ample                                          point                          No. R.sup.1        X                 R.sup.2                                                                            R.sup.3                                                                            (°C.)                   __________________________________________________________________________    6   (CH.sub.3).sub.3 C                                                                           CO                                                                                               ##STR274##                                                                             193 (× 1/2 NDS)          7   (CH.sub.3).sub.3 C                                                                           CO                                                                                               ##STR275##                                                                             40-48                          8   (CH.sub.3).sub.3 C                                                                           CO                                                                                               ##STR276##                                                                             49                             9   (CH.sub.3).sub.3 C                                                                           CO                                                                                               ##STR277##                                                                             201 (× 1/2 NDS)          10  (CH.sub.3).sub.3                                                                             CO                n-C.sub.4 H.sub.9                                                                  C.sub.2 H.sub.5                                                                    Oil                            11  (CH.sub.3).sub. 3 C                                                                          CH(OH)                                                                                           ##STR278##                                                                             151 (Z-form)                   12  (CH.sub.3).sub.3 C                                                                           CH(OH)                                                                                           ##STR279##                                                                             Oil                            13  (CH.sub.3).sub.3 C                                                                           CH(OC.sub.3 H.sub.7n)-                                                                           ##STR280##                                                                             Oil                            14  (CH.sub.3).sub.3 C                                                                            ##STR281##                                                                                      ##STR282##                                                                             Oil                            15  (CH.sub.3).sub.3 C                                                                           CH(OCOCHCl.sub.2)                                                                                ##STR283##                                                                             Oil                            16  (CH.sub.3).sub.3 C                                                                            ##STR284##                                                                                      ##STR285##                                                                             Oil                            17                                                                                 ##STR286##    CH(OH)                                                                                           ##STR287##                                                                             Oil                            18                                                                                 ##STR288##    CH(OH)            C.sub. 2 H.sub.5                                                                   C.sub.2 H.sub.5                                                                    Oil                            19                                                                                 ##STR289##    CH(OH)                                                                                           ##STR290##                                                                             Oil                            20                                                                                 ##STR291##    CH(OCOCH.sub.3)                                                                                  ##STR292##                                                                             Oil                            21  (CH.sub.3).sub.3 C                                                                           CCH.sub.3 (OH)                                                                                   ##STR293##                                                                             101                            22  (CH.sub.3).sub.3 C                                                                           CH(OH)                                                                                           ##STR294##                                                                             154 (.HCl) (Z-form)            23                                                                                 ##STR295##    CH(OH)            C.sub.3 H.sub.7                                                                    CH.sub.3                                                                           Oil                            24  (CH.sub.3).sub.3 C                                                                           CH(OH)                                                                                           ##STR296##                                                                             110 (.CuCl.sub.2) (Z-form)     25                                                                                 ##STR297##    CH(OCONHCH.sub.3)                                                                                ##STR298##                                                                             62                             26                                                                                 ##STR299##    CH(OH)            C.sub.2 H.sub.5                                                                    CH.sub.3                                                                           Oil                            27                                                                                 ##STR300##                                                                                   ##STR301##       C.sub.3 H.sub.7                                                                    CH.sub.3                                                                           Oil                            28                                                                                 ##STR302##    CH(CCOCH.sub.3)   C.sub.3 H.sub.7                                                                    CH.sub.3                                                                           Oil                            29  (CH.sub.3).sub.3 C                                                                            ##STR303##                                                                                      ##STR304##                                                                             Oil (Z-form)                   30  ClCH.sub.2C(CH.sub.3).sub.2                                                                  CO                                                                                               ##STR305##                                                                             51                             31  ClCH.sub.2C(CH.sub.3).sub.2                                                                  CO                                                                                               ##STR306##                                                                             Oil                            32  ClCH.sub.2C(CH.sub.3).sub.2                                                                  CH(OH)                                                                                           ##STR307##                                                                             Oil                            33                                                                                 ##STR308##    CH(OH)                                                                                           ##STR309##                                                                             156                            34  (CH.sub.3).sub.3 C                                                                           CH(OH)                                                                                           ##STR310##                                                                             153 (.HNO.sub.3) (Z-form)      35                                                                                 ##STR311##    CH(OH)                                                                                           ##STR312##                                                                             Oil                            36                                                                                 ##STR313##    CH(OH)                                                                                           ##STR314##                                                                             Oil                            37                                                                                 ##STR315##    CH(OH)                                                                                           ##STR316##                                                                             Oil                            38                                                                                 ##STR317##    CH(OH)            C.sub.2 H.sub.5                                                                    CH.sub.3                                                                           Oil                            39                                                                                 ##STR318##    CH(OH)            C.sub.2 H.sub.5                                                                    CH.sub.3                                                                           Oil                            40                                                                                 ##STR319##    CH(OH)            C.sub.4 H.sub.9                                                                    C.sub.2 H.sub.5                                                                    Oil                            41  ClCH.sub.2C(CH.sub.3).sub.2                                                                  CH(OH)                                                                                           ##STR320##                                                                             Oil                            42  (CH.sub.3).sub.3 C                                                                           CH(OCH.sub.3)                                                                                    ##STR321##                                                                             63 (Z-form)                    43                                                                                 ##STR322##    CH(OH)            C.sub.4 H.sub.9                                                                    C.sub.2 H.sub.5                                                                    Oil                            44  FCH.sub.2C(CH.sub.3).sub.2                                                                   CO                C.sub.4 H.sub.9                                                                    C.sub.2 H.sub.5                                                                    Oil                            45  (CH.sub.3).sub.3 C                                                                           CH(OCH.sub.3)                                                                                    ##STR323##                                                                             104 (E-form)                   46  (CH.sub.3).sub.3 C                                                                           CH(OH)                                                                                           ##STR324##                                                                             137 (.HNO.sub.3) (E-form)      47                                                                                 ##STR325##    CH(OH)            CH.sub.3                                                                           CH.sub.3                                                                           187                            48  ClCH.sub.2C(CH.sub.3).sub.2                                                                  CH(OH)            CH.sub.3                                                                           CH.sub.3                                                                           Oil                            49  (CH.sub.3).sub.3 C                                                                           CH(OH)                                                                                           ##STR326##                                                                             242 (.1/2 NDS) (E-form)        50  (CH.sub.3).sub.3 C                                                                           CH(OH)                                                                                           ##STR327##                                                                             168 (.CuCl.sub.2) (E-form)     51  (CH.sub.3).sub.3 C                                                                           CO                                                                                               ##STR328##                                                                             137-140 (.CuCl.sub.2)                                                         (E-form)                       52                                                                                 ##STR329##    CH(OH)                                                                                           ##STR330##                                                                             157                            53                                                                                 ##STR331##    CH(OH)            C.sub.4 H.sub.9                                                                    C.sub.2 H.sub.5                                                                    118                            54  FCH.sub.2C(CH.sub.3).sub.2                                                                   CO                                                                                               ##STR332##                                                                             Oil                            55  FCH.sub.2C(CH.sub.3).sub.2                                                                   CO                                                                                               ##STR333##                                                                             Oil                            56  FCH.sub.2C(CH.sub.3).sub.2                                                                   CH(OH)                                                                                           ##STR334##                                                                             Oil                            57  FCH.sub.2C(CH.sub.3).sub.2                                                                   CH(OH)                                                                                           ##STR335##                                                                             Oil                            58  FCH.sub.2C(CH.sub.3).sub.2                                                                   CO                                                                                               ##STR336##                                                                             Oil (Z-form)                   59  FCH.sub.2C(CH.sub.3).sub.2                                                                   CO                                                                                               ##STR337##                                                                             Oil (Z-form)                   60  ClCH.sub.2C(CH.sub.3).sub.2                                                                  CO                                                                                               ##STR338##                                                                             103 (E-form)                   61                                                                                 ##STR339##    CH(OH)                      144                            62                                                                                 ##STR340##    CH(OH)            C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                    148                            63  FCH.sub.2C(CH.sub.3).sub.2                                                                   CH(OH)                                                                                           ##STR341##                                                                             n.sub.D.sup.20 : 1,5049                                                       (Z-form)                       64  FCH.sub.2C(CH.sub.3).sub.2                                                                   CH(OH)                                                                                           ##STR342##                                                                             n.sub.D.sup.20 : 1,4910                                                       (Z-form)                       65  ClCH.sub.2C(CH.sub.3).sub.2                                                                  CH(OH)                                                                                           ##STR343##                                                                             n.sub.D.sup.20 : 1,5050                                                       (E-form)                       __________________________________________________________________________     E- and Zform: the two possible geometric isomer forms                         NDS: 1,5naphthalindisulfonic acid                                        

It will be understood that the specification and examples areillustrative, but not limitative of the present invention and that otherembodiments within the spirit and scope of the invention will suggestthemselves to those skilled in the art.

What is claimed is:
 1. 1-Vinyltriazole compound of the formula##STR344## wherein R¹ is alkyl with 1 to 4 carbon atoms, or substitutedalkyl with 1 to 4 carbon atoms wherein the substituent is fluorine orchlorine;R² and R³, together with the carbon atom to which they arebonded, represent cyclohexyl, cyclohexenyl, or methyl substitutedcyclohexenyl;and acid addition salts and metal salt complexes thereofwherein the acid is hydrochloric acid, napthaline-1,5-disulphonic acidor nitric acid and the metal salt is copper chloride.
 2. 1-Vinyltriazolecompound as claimed in claim 1 wherein R¹ is fluorine or chlorinesubstituted alkyl of 1 to 4 carbon atoms.
 3. 1-Vinyltriazole compound asclaimed in claim 1 wherein R² and R³, together with the carbon atom towhich they are bonded, represent cyclohexenyl or methyl substitutedcyclohexenyl.
 4. 1-Vinyltriazole compound as claimed in claim 1 whereinR² and R³, together with the carbon atom to which they are bonded,represent cyclohexyl.
 5. 1-Vinyltriazole compound as claimed in claim 1wherein R¹ is alkyl of 1 to 4 carbon atoms.
 6. 1-Vinyltriazole compoundas claimed in claim 1 in the form of a metal salt complex thereof. 7.Fungicidal composition comprising a compound as claimed in claim 1 inadmixture with a solid or liquefied diluent or carrier containing asurface-active agent.
 8. Fungicidal composition comprising a compound asclaimed in claim 35 containing from 0.1 to 95% of the active compound,by weight.
 9. Method for regulating plant growth, which method comprisesapplying to the plants or their habitat, an effective amount of a1-vinyltriazole compound as claimed in claim
 1. 10. Method as claimed inclaim 9 wherein the active compound is applied to an area of agriculturein an amount of 0.01 to 50 kg per hectare.
 11. Method as claimed inclaim 9 wherein the active compound is applied to an area of agriculturein an amount of 0.05 to 10 kg per hectare.
 12. Method as claimed inclaim 9 wherein the compound is applied in a composition containing from0.0001 to 1% of the active compound by weight.
 13. Method as claimed inclaim 9 wherein the composition used contains from 0.001 to 0.5% of theactive compound by weight.
 14. Method as claimed in claim 9 wherein thecompound is applied to the soil in an amount of 0.0001 to 0.1% byweight.
 15. Method as claimed in claim 9 wherein the compound is appliedto the soil in an amount of 0.0001 to 0.2% by weight.
 16. Method forcombating fungi, which method comprises applying to the fungi, or to ahabitat thereof, a 1-vinyltriazole compound as claimed in claim
 1. 17.Method for combating fungi as claimed in claim 16 wherein the activecompound is applied to an area of agriculture in an amount of 0.01 to 50kg per hectare.
 18. Method for combating fungi as claimed in claim 16wherein the active compound is applied to an area of agriculture in anamount of 0.05 to 10 kg per hectare.
 19. Method for combating fungi asclaimed in claim 16 wherein the composition used contains from 0.0001 to1% of the active compound by weight.
 20. Method for combating fungi asclaimed in claim 16 wherein the compound is applied in a compositioncontaining from 0.001 to 0.5% of the active compound by weight. 21.Method for combating fungi as claimed in claim 16 wherein the compoundis applied to the soil in an amount of 0.00001 to 0.1% by weight. 22.Method for combating fungi as claimed in claim 16 wherein the compoundis applied to the soil in an amount of 0.0001 to 0.2% by weight. 23.1-Vinyltriazole compound 25 designated1-cyclohexyl-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-pent-1-en-3-one. 24.1-Vinyltriazole compound of claim 3 designated1-(cyclohex-3-en-1-yl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-pent-1-en-3-one25. 1-Vinyltriazole compound of claim 3 designated1-(methyl-cyclohex-3-en-1-yl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-pent-1-en-3-one.26. 1-Vinyltriazole compound of claim 3 designatednaphthalene-1,5-disulphonic acid addition salt of1-(cyclohex-3-en-1-yl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-pent-1-en-3-one.27. 1-Vinyltriazole compound of claim 4 designatednaphthalene-1,5-disulphonic acid addition salt of1-cyclohexyl-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-pent-1-en-3-one. 28.1-Vinyltriazole compound as claimed in claim 2, wherein R¹ is fluorineor chlorine substituted tert.-butyl.
 29. 1-Vinyltriazole compound asclaimed in claim 5, wherein R¹ is tert.-butyl.